CN1551909A - Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant - Google Patents

Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant Download PDF

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CN1551909A
CN1551909A CNA028173287A CN02817328A CN1551909A CN 1551909 A CN1551909 A CN 1551909A CN A028173287 A CNA028173287 A CN A028173287A CN 02817328 A CN02817328 A CN 02817328A CN 1551909 A CN1551909 A CN 1551909A
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dispersion
fluoropolymer
surfactant
fluorinated
weight
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CN100369988C (en
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M・C・达达拉斯
M·C·达达拉斯
账箍
R·艾普斯科
乘
F·克鲁斯
哈维
L·W·哈维
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/16—Purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/20—Concentration
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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Abstract

The present invention provides a fluoropolymer dispersion comprising fluoropolymer particles having an average particle size of 10 to 400 nm dispersed in water whereby the dispersion is free of fluorinated surfactant having a molecular weight of less than 1000 g/mol or contains the fluorinated surfactant having a molecular weight of less than 1000 g/mol in an amount of not more than 0.025% by weight based on the total weight of solids in the dispersion. The dispersion further comprises a non-ionic surfactant and an anionic surfactant selected from fluorinated anionic surfactants having a molecular weight of at least 1000 g/mol, non-fluorinated anionic surfactants and mixtures thereof.

Description

Do not contain or contain the fluoropolymer dispersion of a small amount of low molecular weight fluorinated surfactant
Invention field
The present invention relates to not contain or contain the fluoropolymer aqueous dispersion of a small amount of low molecular weight fluorinated surfactant.In specific words, the present invention relates to reduce this kind high solids content and contain the viscosity that nonionic surfactant is the fluoropolymer dispersion of stablizer.
Background of invention
The polymkeric substance that fluoropolymer promptly has a fluorinated backbone is that people understand already, and because some good properties such as thermotolerance, chemical resistant properties, weathering resistance, UV-stability etc. have been used for various application.For example, in " Modern Fluoropolymers " Wiley Science 1997 that John Scheirs edits, various fluoropolymers have been described.Fluoropolymer can have partially fluorinated skeleton, and generally at least 40 weight % fluoridize or complete fluorizated skeleton.The object lesson of fluoropolymer comprises the terpolymer (THV) and the polyvinylidene fluoride polymer (PVDF) of multipolymer (FEP polymkeric substance), perfluoroalkyl alkoxy copolymer (PFA), ethylene-tetrafluoroethylene (ETFE) multipolymer, tetrafluoroethylene, R 1216 and the vinylidene fluoride of polytetrafluoroethylene (PTFE), tetrafluoroethylene (TFE) and R 1216 (HFE).
Fluoropolymer can be used for coated substrate, performance such as chemical resistant properties, weathering resistance, the repellency of base material needs is provided and scolds oiliness etc.For example, the aqueous dispersion of fluoropolymer can be used for coat kitchen ware, impregnate fabric such as glass fabric, coated paper or polymeric substrate.Be economic and convenient consideration, the fluoropolymer solid content of fluoropolymer dispersion is generally between 30-70 weight %.
Generally the method for preparing the fluoropolymer aqueous dispersion of Cai Yonging relates to the aqueous emulsion polymerization of one or more fluorinated monomers, carries out enrichment step subsequently usually, to improve the solid content of the coarse dispersion that obtains after the letex polymerization.The aqueous emulsion polymerization of fluorinated monomer relates generally to use fluorinated surfactant.Normally used fluorinated surfactant comprises Perfluorocaprylic Acid and salt thereof, particularly ammonium perfluorocaprylate.Another kind of spendable fluorinated surfactant comprises perfluoropolyether surfactants, as at EP 1059342, EP 712882, EP 752432, EP 816397, US6103843 and US6126849.Other spendable tensio-active agents are disclosed in US5229480, US5763553, US5668884, US5700859, US5804650, US5895799, WO 00/22002 and WO 00/71590.
This class fluorinated surfactant of great majority has lower molecular weight, and promptly molecular weight is less than 1000 gram/moles.Recently, low-molecular-weight like this fluorinated compound has caused the concern of people to environment.Therefore, take measures, from aqueous dispersion, fully phase out low-molecular-weight fluorinated surfactant or the low molecular weight fluorinated surfactant to major general's aqueous dispersion minimizes.For example, WO 96/24622 and WO 97/17381 disclose a kind of aqueous emulsion polymerization and prepare fluoropolymer, just can not carry out polyreaction thereby do not need to add fluorinated surfactant.The opposing party and, US 4369266 discloses a kind of method, by ultrafiltration remove the part fluorinated surfactant.Latter event, fluoropolymer solids has also increased in the dispersion, promptly concentrates this dispersion simultaneously removing fluorinated surfactant.WO 00/35971 also discloses a kind of method, contacts with anionite by fluoropolymer dispersion, reduces the fluorinated surfactant amount.
Because just the coarse dispersion solid content after letex polymerization has been generally at maximum 35 weight %, thus this coarse dispersion is gone up concentrated, to improve its solid content.Concentrate usually at stablizer for keeping the stability of dispersion, going up, particularly nonionic surfactant carries out under existing as stablizer.
Yet, go up when concentrating when the fluoropolymer dispersion that does not contain or only contain a small amount of low-molecular-weight fluorinated surfactant, find that cause viscosity to increase, this is undesirable.And upward the dispersion that the stability of spissated dispersion is higher than low-molecular-weight fluorinated surfactant amount under certain condition is poor.Therefore, require to solve one or more above-mentioned defectives in prior art field.
Summary of the invention
On the one hand, the invention provides a kind of fluoropolymer dispersion, comprising the mean particle size that is dispersed in the water is the particles of fluoropolymer of 10-400nm, this dispersion does not contain the fluorinated surfactant of molecular weight less than 1000 gram/moles, or be benchmark in total weight of solids in the dispersion, contain the molecular weight that is no more than 0.025 weight % fluorinated surfactant less than 1000 gram/moles.Dispersion also comprises a kind of nonionic surfactant and is selected from the anion surfactant of fluorinated anionic tensio-active agent, non-fluorinated anionic surfactant and their mixture that molecular weight is at least 1000 gram/moles.
Second aspect the invention provides the method that the particles of fluoropolymer dispersion is provided, and this method comprises the following steps:
-provide fluoropolymer dispersion, this dispersion to comprise the particles of fluoropolymer that mean particle size is 10-400nm, comprise molecular weight less than the fluorinated surfactant of 1000 gram/moles or do not contain this tensio-active agent;
If-fluorinated surfactant greater than being benchmark with the dispersion total weight of solids, is 0.025 weight % of benchmark with fluoropolymer solids gross weight in the dispersion better, reduce the fluorinated surfactant amount of dispersion;
-in the presence of the nonionic surfactant, concentrate fluoropolymer dispersion, improve the amount of fluoropolymer solids in the dispersion;
-before or after last concentrated fluoropolymer dispersion, add a kind of anion surfactant in fluoropolymer dispersion, described anion surfactant is selected from fluorinated anionic tensio-active agent, non-fluorinated anionic surfactant and their mixture of molecular weight at least 1000 gram/moles.
The third aspect the invention provides the method with above-mentioned fluoropolymer dispersion coated substrate of the present invention.
Detailed description of the Invention
According to the present invention, find, if fluoropolymer contains anion fluorinated surfactants, anion fluorinated surfactants of molecular weight at least 1000 gram/moles (below be called high molecular fluoridize tensio-active agent) or their mixture, can make contain nonionic surfactant and do not contain low molecular weight fluorinated surfactant or contain a small amount of as less than 0.025 weight % low molecular weight fluorinated surfactant (in total weight of solids, specifically be fluoropolymer solids gross weight meter in the dispersion) the viscosity of fluoropolymer dispersion improve to reduce, or avoid this viscosity to improve.And, can also improve the stability of fluoropolymer dispersion by adding anionic non-fluorinated surfactants or anionic polymer amount fluorinated surfactant.
The preferred anionic surfactants non-fluorinated surfactants is to have pKa to be not more than 4, better is not more than the tensio-active agent of 3 acid groups.Find that such anion surfactant generally can also improve the stability of fluoropolymer dispersion except controlling viscosity.The example of non-fluorinated anionic surfactant comprises the tensio-active agent that contains one or more anionic groups.The negatively charged ion non-fluorinated surfactants can comprise except one or more anionic groups are arranged, also have other hydrophilic radical as the polyalkylene oxide groups such as the polyoxyethylene groups of 2-4 carbon atom are arranged on its oxyalkylene group, or as the tensio-active agent of the group of amino.In addition, when containing amino in the tensio-active agent, the pH of dispersion should not make amino be in protonated form.Typical non-fluorinated surfactants comprises negatively charged ion hydrocarbon tensio-active agent.Term " negatively charged ion hydrocarbon tensio-active agent " comprises this class tensio-active agent at this, one or more hydrocarbyl portions is arranged in its molecule and one or more anionic groups particularly acid groups such as sulfonic acid, sulfuric acid, phosphoric acid or hydroxy-acid group and its salt are arranged.The example of the hydrocarbyl portion of negatively charged ion hydrocarbon tensio-active agent comprises saturated and undersaturated aliphatic group, and for example 6-40 carbon atom arranged, and better is 8-20 carbon atom.Such aliphatic group can be a straight or branched, can contain ring structure.Hydrocarbyl portion also can be aromatics or contain aromatic group.In addition, hydrocarbyl portion can contain one or more heteroatomss such as oxygen, nitrogen and sulphur.
The object lesson of the negatively charged ion hydrocarbon tensio-active agent that the present invention uses comprises alkylsulfonate such as lauryl sulfonate, alkyl-sulphate such as lauryl sulfate, alkylaryl sulphonate and alkyl aryl sulfate, fat (carboxylic acid) acid and salt thereof such as lauric acid and salt and alkyl acid phosphate or alkyl aryl ester and salt thereof.Commercially available negatively charged ion hydrocarbon tensio-active agent comprises the EmulsogenTM LS (Sodium Lauryl Sulphate BP/USP) that can buy from Clariant GmbH and EmulsogenTM EPA 1954 (C12-C14 sodium alkyl sulfate mixture) and the TRITONTM X-200 (alkyl sodium sulfonate) that can buy from Union Carbide.Be preferably the anion surfactant of sulfonic acid group.
The anion surfactant of the nonfluorinated that other is suitable comprises the silicone base tensio-active agent, if any the polydialkysiloxane of negatively charged ion side group such as phosphate, carboxyl, sulfonic group and sulfate and salt thereof.
Except non-fluorinated anionic surfactant or as an alternative thing can also use high molecular to fluoridize tensio-active agent.The molecular weight that high molecular is fluoridized tensio-active agent is at least 1000 gram/moles, better at least 1200 gram/moles.High molecular weight anionic and fluorizated tensio-active agent comprise polymeric surfactant, include the PFPE of one or more anionic groups such as carboxyl or its salt.The perfluoropolyether surfactants example comprises following general formula (I) or those tensio-active agents (II):
R f a-O-(CF 2O) k(CF 2CF 2O) p(CF(CF 3)CF 2O) q-Q 1-COOM (I)
MOOC-Q 1-O-(CF 2O) k(CF 2CF 2O) p(CF (CF 3) CF 2O) q-Q 2-COOZ (II) wherein, k, p and q represent the value of 0-15 separately, 0-10 or 12 normally, k, p and q's and for making number-average molecular weight be at least 1000 gram/moles, R f aRepresentative better has the perfluoroalkyl of 2-4 carbon atom, and M and Z represent hydrogen or positively charged ion independently of one another, better are univalent cation such as ammonium or alkalimetal ion, Q 1And Q 2Representative-CF independently of one another 2-or-CF (CF 3)-.
The example of the fluorinated surfactant of general formula (II) comprises corresponding to those of following formula:
R f a-O-(CFXCF 2O) r-CFX-COOM (III) wherein, R f aHave and the identical definition of general formula (II) with M, X is hydrogen atom or fluorine atom, and the value of r makes the molecular weight of tensio-active agent be at least 1000 gram/moles.Such fluorinated surfactant example is disclosed in EP 219065.
Spendable also have a kind of fluorinated surfactant to comprise the (per) fluoropolymer that comprises the following formula repeating unit:
Wherein, s is 0,1 or 2, and t is the integer of 2-4, and G is the part that contains one or more anionic groups.The example of suitable anionic group comprises: carboxyl, as-CO 2M, wherein, M can be that hydrogen, unit price or divalent-metal ion (as sodium, potassium or magnesium), ammonium are (as single ammonium, tetra-allkylammonium, four aryl ammonium) Huo Phosphonium (as Si Wan Ji Phosphonium); Or sulfonic acid group, as-SO 3M, wherein the definition of M as mentioned above.Preferably, the fluorinated polymer tensio-active agent is to have from tetrafluoroethylene units and the unitary multipolymer of general formula (IV).Such multipolymer and preparation method thereof is disclosed in for example US 5608022 and WO 00/52060.Suitable fluorinated surfactant has, from E.I.duPont de Nemours﹠amp; Co., the NafionTM super acid catalyzer that Wilmington, DE buy, from Asahi Chemical Co., the FlemionTM super acid polymkeric substance that Osaka, Japan buy and from Asahi Glass Co., the AcipexTM super acid polymkeric substance that Tokyo, Japan buy.
The anion surfactant amount that adds in the fluoropolymer dispersion generally depends on the property quality and quantity of the nonionic surfactant that exists in the character, fluoropolymer quality and quantity, dispersion of fluorinated surfactant and the property quality and quantity that is present in the low molecular weight fluorinated surfactant in the fluoropolymer dispersion.Usually, be benchmark in fluoropolymer solids weight in the dispersion, the anion surfactant amount is generally 10-5000ppm, is preferably 100-3000ppm, more preferably 100-2500ppm.When the anion surfactant consumption was too low, still can observe the viscosity of not expecting increased.On the other hand, when the anion surfactant amount was too high, viscosity also can rise.If also need to improve the stability of dispersion, must use the anion surfactant of the 2000ppm that is at least fluoropolymer solids weight meter.Those of ordinary skill in the art just can easily determine the optimum concn of anion surfactant in the dispersion by normal experiment.
When low molecular weight fluorinated surfactant exists, can be the arbitrary low molecular weight fluorinated surfactant that uses in the fluorinated monomer letex polymerization, comprise those tensio-active agents described in the description of the Prior Art.Low molecular weight fluorinated surfactant commonly used can be a telogen, comprises corresponding to those of following general formula:
Y-R f-Z-M (V) wherein, Y represents hydrogen, Cl or F; R fRepresentative has the straight or branched perfluorination alkylidene group of 4-10 carbon atom; Z represents COO -Or SO 3 -, M represents univalent cation such as alkalimetal ion or ammonium ion.
When low molecular weight fluorinated surfactant is present in the fluoropolymer dispersion, be benchmark in the dispersion solid amount, it is measured less than 0.025 weight %, is not more than 0.01 weight % preferably, preferably is not more than 50ppm.
Fluoropolymer dispersion of the present invention also comprises nonionic surfactant.Nonionic surfactant generally is non-fluorizated nonionic surfactant.Usually, nonionic surfactant is to contain one or more tensio-active agents that are connected the hydrocarbon part on the nonionic hydrophilic radical, and the nonionic hydrophilic radical generally comprises the oxyethylene group that its alkylidene group has 2,3 or 4 carbon atoms.As mentioned above.For example, the nonionic hydrophilic radical can be polyoxyethylene groups, polyoxypropylene base or a kind of multipolymer, comprises segmented copolymer, comprises oxygen ethene and oxypropylene group.According to specific embodiments of the present invention, nonionogenic tenside is corresponding to following formula:
R 1-O-[CH 2CH 2O] n-[R 2O] m-R 3(VI) wherein, R 1Representative has the aryl or the aliphatic group of at least 8 carbon atoms, R 2Representative has the alkylidene group of 3 carbon atoms, R 3Represent hydrogen or C1-C3 alkyl, n is the value of 0-40, and m is the 0-40 value, n+m and be at least 2.
Should be understood that in the following formula (VI), can occur by block by the unit of n and m mark, or they with configuration alternately or arbitrarily configuration exist.
The nonionic surfactant example of general formula (VI) comprises the alkylphenol oxygen ethide of following formula:
Figure A0281732800081
Wherein, R 1Be the alkyl of 4-20 carbon atom, r represents the value of 4-20.The example of the tensio-active agent of general formula (VII) comprises ethoxylation p-isooctyl phenol, and for example TRITONTMX 100 (the ethoxy unit number is about 10) or TRITONTMX 114 (the ethoxy unit number is about 7-8) buy with TRITONTM series.
Other example comprises R in the following formula (VII) 1Represent the alkyl of 4-20 carbon atom, m is 0, R 3Be those of hydrogen.Its example includes the different tridecyl alcohol of the ethoxylation of 8 oxyethyl groups, can buy from Clariant GmbH by GENAPOL X 080.Can also use the nonionic surfactant of general formula (VI), wherein, wetting ability partly comprises the segmented copolymer of oxyethyl group and propoxy-.Such nonionogenic tenside can GENAPOL PF 40 and GENAPOL PF 80 buy from Clariant GmbH.
The amount of nonionic surfactant in fluoropolymer dispersion with respect to total weight of solids in the fluoropolymer dispersion, is generally 1-12 weight %.Be 3-10 weight % preferably.
The fluoropolymer that comprises in the fluoropolymer dispersion is to have polymkeric substance partially fluorinated or the perfluorination skeleton.Usually, fluoropolymer is that its skeleton at least 40 weight % fluoridize, and better at least 50 weight % fluoridize, better at least 60 weight % fluorizated polymkeric substance.Fluoropolymer can also have the perfluorination skeleton for example in PTFE.Fluoropolymer can be homopolymer or multipolymer, and dispersion can contain the mixture of different fluoropolymers.The fluoropolymer example comprises following multipolymer: can be by the tetrafluoroethylene base of melt, especially tetrafluoroethylene/hexafluoropropylene, tetrafluoroethylene/perfluoro (alkyl vinyl) ether, perfluoroalkyl has the multipolymer of 1 to 5 carbon atom, particularly tetrafluoroethylene/perfluoro (n-propyl-vinyl) ether, tetrafluoroethylene/ethylene, tetrafluoroethylene base/trifluorochloroethylene, trifluorochloroethylene/ethene, tetrafluoroethylene/vinylidene fluoride and R 1216/vinylidene fluoride; The terpolymer of tetrafluoroethylene/perfluoro (alkyl vinyl) ether/R 1216, tetrafluoroethylene/ethylene/R 1216 and tetrafluoroethylene/vinylidene fluoride/R 1216; Or the tetrapolymer of tetrafluoroethylene/vinylidene fluoride/R 1216/perfluor (alkyl vinyl) ether and tetrafluoroethylene/ethylene/R 1216/perfluor (alkyl vinyl) ether.The fluoropolymer that can be used for this dispersion also has fluorinated ethylene propylene, poly(vinylidene fluoride) and voltalef.It can not promptly be homopolymer from the polymkeric substance of melt such as tetrafluoroethylene processing that dispersion can also comprise, and can also choose wantonly and comprise a small amount of (0.1-3 mole %) modified copolymer monomer, as R 1216 or perfluor (alkyl vinyl) ether or trifluorochloroethylene.
The mean particle size of fluoropolymer (median size) is generally in 10-400nm scope 25-400nm more fortunately in the dispersion.Median size is generally measured by dynamic light scattering, and determines number average bead diameter thus.Dispersion can be unimodality and multimodal attitude such as bimodal attitude.The fluoropolymer amount is at least 30 weight %, for example 35-70 weight % usually in the dispersion.
Fluoropolymer can be used for coated substrate.For example, fluoropolymer dispersion can be used for coat metal substrates, polymeric substrate such as polyester and polypropylene base or coated paper.Fluoropolymer dispersion also can be used for applying or impregnate fabric, particularly fiberglass substrate.Before the coating, fluoropolymer dispersion can also other component mix, and prepares the coating composition that specific application requires.For example, fluoropolymer dispersion and polyamidoimide and Polyphenylene Sulfone mixed with resin provide anti-stick coating on base material, disclose as WO 94/14904.Another kind of coating composition comprises mineral filler such as colloidal silica, aluminum oxide, and mineral dye, discloses as EP 22257 and US 3489595.
Fluoropolymer dispersion generally can obtain by the so-called coarse dispersion that the fluorinated monomer letex polymerization produces.If do not having to carry out polymerization under the low molecular weight fluorinated surfactant, such dispersion does not contain low molecular weight fluorinated surfactant, but generally can comprise the low molecular weight fluorinated surfactant of fundamental quantity.If low molecular weight fluorinated surfactant concentration is greater than the amount that requires in the dispersion,, should remove to this class tensio-active agent of small part as 0.025 weight %.
According to an embodiment, reduce the low molecular weight fluorinated surfactant amount, in fluoropolymer dispersion, can add aforesaid nonionic surfactant, then, fluoropolymer dispersion contacts with anionite.This quadrat method is disclosed in WO 00/35971.Suitable anionite comprises the counter ion that are at least 3 acid corresponding to the pKa value.
Anion exchange procedures should carried out under the alkaline condition substantially.Therefore, ion exchange resin is preferably OH -Form is although also can use corresponding to faintly acid negatively charged ion such as fluorochemical or oxalate.The concrete alkalescence of ion exchange resin is very unimportant.Preferred strong alkali resin is because strong alkali resin can efficiently be removed low molecular weight fluorinated surfactant.This process can be undertaken by fluoropolymer is contained in the tower of ion exchange resin by one, and perhaps, fluoropolymer dispersion stirs with ion exchange resin, afterwards by the filtering separation fluoropolymer dispersion.Adopt this method, the low molecular weight fluorinated surfactant amount can be reduced to 150ppm, even is lower than 10ppm.Therefore, can obtain to be substantially free of the dispersion of low molecular weight fluorinated surfactant.
At low molecular weight fluorinated surfactant is its free acid form, is the situation of steam-volatile matter, can adopt the amount that reduces low molecular weight fluorinated surfactant in the following method.By in the fluoropolymer aqueous dispersion, adding nonionic surfactant, the pH value of fluoropolymer aqueous dispersion is less than 5, distillation removes devaporation-volatility fluorinated surfactant and reaches required value up to the steam-concentration of volatility fluorinated surfactant in dispersion, and steam-volatile fluorinated surfactant is removed from the aqueous dispersion of fluoropolymer with its free acid form.The low molecular weight fluorinated surfactant that can adopt this method to remove comprises the tensio-active agent of for example going up formula V.
Generally, require to improve the amount of fluoropolymer solids in dispersion.Improve the fluoropolymer solids amount, can adopt any concentration method of going up.Last concentration method generally carries out in the presence of nonionic surfactant, adds nonionic surfactant and stablize this dispersion in last concentration process.The nonionic surfactant amount is measured in dispersion and is generally 1-12 weight %, and better 3-10 weight % concentrates to go up.Go up spissated appropriate method comprise on ultrafiltration, the heat concentrate, hot decantation and electric decantation, disclose as GB 642025.
Hyperfiltration process comprises following step: (a) add nonionic surfactant in the dispersion of hyperconcentration and (b) in semi-permeable this dispersion of ultra-filtration membrane cocycle, be separated into fluorinated polymer dispersion concentration thing and moisture penetrating fluid on will carrying out.The logical general service pump of this circulation carries out with 2-7 meter per second transfer rate, keeps not participant of fluorinated polymer to cause the component contact of frictional force.Advantage in addition of this hyperfiltration process is between last diakinesis, also to have removed the part low molecular weight fluorinated surfactant.Therefore, adopt this hyperfiltration process can reduce low molecular weight fluorinated surfactant amount and upward concentrated this dispersion simultaneously.
Increase the fluoropolymer solids of aqueous dispersion, can also adopt hot decantation.In this method, on needs, add nonionic surfactant in the spissated dispersion, then, dispersion heating with form can decantation supernatant liquid, this layer clear liquid comprises water and some nonionogenic tensides usually, and another layer comprises spissated dispersion.This method is disclosed in for example US 3037953 and EP 818506.
Concentrate on the heat and relate to the heating dispersion also under reduced pressure except that anhydrating, up to meeting the requirements of concentration.
According to the present invention,, before or after last concentrating, add anion surfactant with control viscosity according to the last concentration method that adopts.For example, if adopt ultrafiltration, general preferred adding anion surfactant, go up subsequently concentrated, to avoid the loss in the ultrafiltration.If adopt heat to go up concentration method, can also can after last concentrating, add anion surfactant before last the concentrating.
Embodiment
Abbreviation:
The PTFE=tetrafluoroethylene
The APFOA=ammonium salt of perfluorooctanoic acid
TRITONTM X-100=ethoxylation is to the isooctyl phenol nonionic surfactant
EMULSOGENTM LS=Sodium Lauryl Sulphate BP/USP
TRITONTM X-200=alkyl aryl polyether sodium sulfonate
Test method:
Use Brookfield Rrookfield DV-III, spindel 86, under 20 ℃ and 20D/l/s, measure the viscosity of dispersion.
Stability test
Fluoropolymer dispersion mixes with the interpolation component and stirs to prepare the disclosed coating composition of EP894541.For this reason, fluoropolymer dispersion mixes with the waterborne compositions that contains polyamide-imide resin (PAI), and making fluoropolymer solids and PAI solid weight ratio is 1: 1.
Use paddle agitator, mix with 800rpm.The time of start-of-record flocculation.
Comparative example 1
By the fluoropolymer dispersion of letex polymerization acquisition PTFE, the fluoropolymer granularity is about 220nm, and solid content is 23 weight %.The TRITONTM X-100 that in this dispersion, adds 6 weight %.In the total dispersion weight is benchmark, and dispersion contains the 0.1 weight %APFOA that has an appointment (=in polymer solids 4350ppm).By ultrafiltration, upward concentrating this dispersion to PTFE amount of solid is 60 weight %.The dispersion viscosity that makes is 20mPa.
Comparative example 2
Repeat the step of comparative example 1, difference is that the dispersion that obtains after the letex polymerization contacts with anionite-exchange resin, and APFOA amount in the dispersion is reduced to 7ppm (is benchmark in the total dispersion weight).This dispersion concentrates according to comparative example 1 described going up then.Find that dispersion viscosity rises to 101mPa.For applying such as metal base or woven fiber glass, viscosity is too high owing to form bubble for this dispersion.
Embodiment 1
Adding EMULSOGENTMLS in the dispersion that obtains after concentrating on comparative example 2, is that benchmark reaches 2000ppm with its amount of solid.Thereby dispersion viscosity drops to 16.7mPa.The dispersion that obtains is fit to apply for example metal base.
Embodiment 2
Adding TRITONT M X-200 in the dispersion that obtains after concentrating on comparative example 2, is that benchmark reaches 1500ppm with its amount of solid.Thereby dispersion viscosity drops to 18mPa.The dispersion that obtains is fit to apply for example metal base.
Comparative example 3
In the presence of 5%TRITONT M X-100, will have on the dispersion of APFOA of 7ppm to be concentrated into 58% solid.The stability of the dispersion that test obtains.Flocculate at once.
Embodiment 3
According to embodiment 1 preparation dispersion, but difference is to use the EMULSOGENTMLS of 1500ppm.Flocculate after about 1 hour.
Embodiment 4
According to embodiment 1 preparation dispersion, but difference is to use the EMULSOGENTMLS of 3000ppm.Stir down and do not flocculate at least 20 hours.
Comparative example 4
Preparation contains the APFOA (is benchmark in the dispersion total weight of solids) of 7ppm and in the dispersion of 8.5 weight % nonionic surfactants of total weight of solids.In total dispersion weight, this dispersion amount of solid is 59 weight %.This dispersion viscosity is 275mPa, and the result is because entrapped air and can not coated glass cloth.
Embodiment 5
According to the dispersion of comparative example 4 preparation PTFE, and the EMULSOGENTMLS of adding 3000ppm (is benchmark in the solid amount).This dispersion viscosity only is 37mPa, can coated glass cloth, and do not have entrained air.

Claims (14)

1. fluoropolymer dispersion, comprising the mean particle size that is dispersed in the water is the particles of fluoropolymer of 10-400nm, described dispersion does not contain the fluorinated surfactant of molecular weight less than 1000 gram/moles, or the content of this tensio-active agent is not more than 0.025 weight % in the total weight of solids of described dispersion, described dispersion also comprises nonionic surfactant, it is characterized in that described dispersion contains and is selected from the fluorinated anionic tensio-active agent that molecular weight is at least 1000 gram/moles, the anion surfactant of non-fluorinated anionic surfactant and their mixture.
2. fluoropolymer dispersion as claimed in claim 1 is characterized in that, in total weight of solids in the dispersion, the anion surfactant amount is 100-5000ppm.
3. fluoropolymer dispersion as claimed in claim 1 or 2 is characterized in that, anion surfactant comprises and contains the non-fluorinated anionic surfactant that pKa is lower than 4 acidic-group.
4. each described fluoropolymer dispersion of claim as described above is characterized in that described dispersion liquid comprises the described particles of fluoropolymer at least 30 weight % of total dispersion weight.
5. fluoropolymer dispersion as claimed in claim 4 is characterized in that, the particles of fluoropolymer amount is 35-70 weight %.
6. each described fluoropolymer dispersion of claim as described above is characterized in that, non-ionic emulsifier is corresponding to following formula:
R 1-O-[CH 2CH 2O] n-[R 2O] m-R 3(VI) wherein, R 1Representative has the aromatics or the aliphatic hydrocarbyl of at least 8 carbon atoms, R 2Representative has the alkylidene group of 3 carbon atoms, R 3Represent hydrogen or C 1-C 3Alkyl, n are the value of 0-40, and m is the 0-40 value, n+m and be at least 2.
7. each described fluoropolymer dispersion of claim as described above is characterized in that in total weight of solids in the dispersion, the non-ionic emulsifier amount is 1-12 weight %.
8. each described fluoropolymer dispersion of claim as described above is characterized in that described particles of fluoropolymer comprises the fluoropolymer of tetrafluoroethylene and/or melt processible.
9. the method for particles of fluoropolymer dispersion is provided, may further comprise the steps:
-provide fluoropolymer dispersion, this dispersion to comprise the particles of fluoropolymer that mean particle size is 10-400nm, comprise molecular weight less than the fluorinated surfactant of 1000 gram/moles or do not contain this tensio-active agent;
If the amount of-described fluorinated surfactant with the dispersion total weight of solids be benchmark greater than 0.025 weight %, reduce the described fluorinated surfactant amount of described dispersion;
-in the presence of the nonionic surfactant, concentrate fluoropolymer dispersion, improve the amount of fluoropolymer solids in the described dispersion;
-before or after last concentrated described fluoropolymer dispersion, add a kind of anion surfactant in fluoropolymer dispersion, described anion surfactant is selected from fluorinated anionic tensio-active agent, non-fluorinated anionic surfactant and their mixture of molecular weight at least 1000 gram/moles.
10. method as claimed in claim 9 is characterized in that, adopts ultrafiltration or heat to go up to concentrate to carry out described going up and concentrate.
11. each described method of claim is characterized in that as described above, in the presence of nonionic surfactant, contacts with anionite-exchange resin by making fluoropolymer dispersion, and the fluorinated surfactant amount is reduced to less than 0.025 weight %.
12. method as claimed in claim 10 is characterized in that the step of enrichment step and the described fluorinated surfactant amount of reduction is carried out simultaneously.
13. the method for coated substrate comprises with the described fluoropolymer dispersion of arbitrary claim among the claim 1-8 applying described base material.
14. method as claimed in claim 10 is characterized in that, described base material is selected from metal base, glasscloth, polymeric substrate and paper.
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